TW201516116A - Hot-melt adhesive sheet for stacked polishing pad and adhesive-layer-bearing support layer for stacked polishing pad - Google Patents

Abstract

The purpose of the present invention is to provide a hot-melt adhesive sheet for a stacked polishing pad wherein a polishing layer is resistant to detachment from a support layer even when high temperatures are produced by long periods of polishing. This hot-melt adhesive sheet is used to laminate a polishing layer to a support layer, and the hot-melt adhesive is a polyester-based hot-melt adhesive that, for each 100 weight parts of a polyester-resin base polymer, contains 2 to 10 weight parts of an epoxy resin that has at least two glycidyl groups per molecule.

Description

Hot-melt adhesive sheet for laminated polishing pad and support layer with adhesive layer for laminated polishing pad (2) Field of invention

The present invention relates to a method for producing stable and high-grinding materials capable of high surface flatness such as optical materials such as lenses and mirrors, or glass substrates for hard disks, aluminum substrates, and general metal polishing processes. The heat-fusible adhesive sheet of the laminated polishing pad which is planarized by the efficiency, and the support layer with the adhesive layer for the laminated polishing pad.

Background of the invention

When manufacturing a semiconductor device, a conductive thin film is formed on the surface of the wafer, and a step of forming a wiring layer by lithography, etching, or the like, or a step of forming an interlayer insulating film on the wiring layer, and the like are performed, and Concavities and convexities formed by a conductor such as a metal or an insulator are formed on the surface of the circle. In recent years, in order to increase the density of semiconductor integrated circuits, the miniaturization of wiring or multilayer wiring has been progressing, but the technique of flattening the unevenness on the surface of the wafer has also become important.

In the past, the polishing pad used for high-precision polishing generally uses a polyurethane resin foam sheet. However, although the polyurethane resin foam sheet has a good local flattening ability, but the cushioning property is insufficient, it is difficult to apply a uniform average pressure on the wafer. force. Therefore, a soft buffer layer is usually provided on the back surface of the polyurethane resin foam sheet as a laminated polishing pad for polishing.

However, the conventional laminated polishing pad generally bonds the polishing layer and the buffer layer with double-sided tape, but the slurry in the polishing penetrates between the polishing layer and the buffer layer to reduce the durability of the double-sided tape, and the polishing layer and the buffer layer become It is easy to cause the problem of peeling.

For example, the following techniques are proposed as a method for solving the above problems.

Patent Document 1 discloses the use of a reactive hot melt adhesive followed by a plastic film and a polishing pad.

In Patent Document 2, the underlayer and the polishing layer are disclosed by a hot-melt adhesive layer followed by a polishing pad.

In Patent Document 3, a polishing pad and a base layer are provided with a polishing pad followed by a double-sided tape, and a hot-melt adhesive is formed between the inside of the polishing layer and the double-sided tape to block the polishing slurry. The technology of the water layer.

Patent Document 4 discloses a polishing pad in which an abrasive layer and a lower layer are joined by a hot melt adhesive containing EVA.

However, the hot-melt adhesives described in Patent Documents 1 to 4 have low heat resistance and have a problem that the polishing layer and the buffer layer are easily peeled off when the high temperature is caused by polishing for a long period of time.

Advanced technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-224944

Patent Document 2: Japanese Laid-Open Patent Publication No. 2005-167200

Patent Document 3: Japanese Laid-Open Patent Publication No. 2009-95945

Patent Document 4: Japanese Patent Publication No. 2010-525956

Summary of invention

An object of the present invention is to provide a hot-melt adhesive sheet for a laminated polishing pad (hereinafter also referred to as a hot-melt adhesive sheet) which is less likely to be peeled off between the polishing layer and the support layer even when it is heated to a high temperature for a long period of time, and A support layer (hereinafter, also referred to as a support layer with an adhesive layer) to which an adhesive layer for a polishing pad is laminated is attached.

In order to solve the above problems, the inventors of the present invention have found that the above object can be attained by the hot-melt adhesive sheet or the support layer with an adhesive layer as described below, and the present invention has been completed.

That is, the present invention relates to a hot-melt adhesive sheet for a laminated polishing pad, which is used for laminating an abrasive layer and a support layer, wherein the hot-melt adhesive is a polyester-based hot-melt adhesive, and is relative to 100 parts by weight of the polyester resin of the base polymer contains 2 to 10 parts by weight of an epoxy resin having 2 or more epoxy propyl groups per molecule.

When the amount of the epoxy resin added is less than 2 parts by weight, the high-temperature polishing sheet has insufficient durability against the "displacement" generated during polishing, so the polishing layer and the support layer are insufficient. It becomes easy to peel off. On the other hand, when it is more than 10 parts by weight, the hardness of the adhesive layer changes. If it is too high, the adhesion is lowered, so that the polishing layer and the support layer become easily peeled off.

The polyester resin of the base polymer is preferably a crystalline polyester resin. borrow By using a crystalline polyester resin, the chemical resistance to the slurry can be improved, and the adhesion of the adhesive layer is not easily lowered.

Moreover, the polyester-based hot melt adhesive has a melting point of 100 to 200 ° C, which is The weight is 1.1 to 1.3, and the melt flow index is preferably 16 to 26 g/10 min at 150 ° C and a load of 2.16 kg.

The hot melt adhesive sheet is preferably a double-sided tape, which is implemented The substrate which is easily treated is provided on both sides with an adhesive layer formed of the aforementioned hot melt adhesive. The aforementioned easy subsequent treatment is preferably corona treatment or plasma treatment. By performing easy subsequent treatment on both surfaces of the substrate, excellent adhesion can be obtained even when the temperature is high due to long-time polishing.

Moreover, the present invention relates to a support layer having an adhesive layer for a build-up polishing pad, which has a binder layer coated with a polyester-based hot-melt adhesive and hardened on one side of the support layer, and The polyester-based hot-melt adhesive contains 2 to 10 parts by weight of an epoxy resin having two or more epoxy propyl groups per molecule, based on 100 parts by weight of the polyester resin of the base polymer. By directly coating and hardening the hot-melt adhesive on the support layer, a support layer with an adhesive layer which is not easily peeled off from the support layer and the adhesive layer is obtained.

The polyester resin of the base polymer is preferably a crystalline polyester resin. By using the crystalline polyester resin, the chemical resistance to the slurry can be improved, and the adhesion of the adhesive layer is not easily lowered.

Moreover, the melting point of the polyester-based hot melt adhesive is 100 to 200 ° C, which is The weight is 1.1~1.3, and the melt flow index should be 16~26g/10min under the condition of temperature 150 °C and load 2.16 kg.

The support layer is preferably provided on the surface provided with the foregoing adhesive layer A polyurethane foam sheet having a skin layer. By using a polyurethane foam sheet having a skin layer as a support layer, an adhesive layer having a uniform thickness and excellent surface smoothness can be formed on the support layer.

The aforementioned polyurethane foam sheet is preferably formed by thermosetting polyurethane to make. When the hot-melt adhesive is applied to the support layer, since the hot-melt adhesive is melted at a high temperature, it is preferable to use a thermosetting polyurethane as a raw material of the support layer from the viewpoint of heat resistance.

By using the hot-melt adhesive sheet of the present invention or the support layer with the adhesive layer, it is possible to obtain a "displacement" of the hot-melt adhesive sheet during polishing even when it is heated to a high temperature due to long-time polishing. A laminated polishing pad which is also improved in durability and which is not easily peeled off between the polishing layer and the support layer.

Used to implement the type of invention

The polishing layer of the present invention has a foam of fine bubbles, and is not particularly limited except for the conditions. For example, polyurethane resin, polyester resin, polyamide resin, acrylic resin, polycarbonate resin, halogen resin (polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, etc.), polystyrene , olefin resin (polyethylene, polypropylene, etc.), epoxy resin, photosensitive tree One type or a mixture of two or more types of fats. The polyurethane resin is particularly suitable as a material for forming a polishing layer because it has excellent abrasion resistance and can easily produce a polymer having desired physical properties by various changes in the composition of the raw material. Hereinafter, a polyurethane resin will be described as a representative of the above foam.

The polyurethane resin is composed of an isocyanate component, a polyol component (high molecular weight polyol, a low molecular weight polyol), and a chain extender.

The isocyanate component may not be particularly limited to the use of a compound known in the field of polyurethanes. Examples of the isocyanate component include toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, and 2,4'-diphenylmethane diisocyanate. An aromatic diisocyanate such as 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, isophthalic diisocyanate, p-indene diisocyanate or meta-diisocyanate; ethylene diisocyanate, Aliphatic diisocyanate such as 2,2,4-trimethylhexamethylene diisocyanate or 1,6-hexamethylene diisocyanate; 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexyl An alicyclic diisocyanate such as methane diisocyanate, isophorone diisocyanate or norbornane diisocyanate. One type may be selected from the above, or two or more types may be mixed.

High molecular weight polyols are exemplified in the field of polyurethanes. For example, polyether polyols typified by polytetramethylene ether glycol, polyethylene glycol, etc., polyester polyols represented by polybutylene adipate, polycaprolactone polyols, A polyester polycarbonate polyol exemplified by a reaction product of a polyester diol such as polycaprolactone and a alkylene carbonate, and a reaction mixture obtained by reacting an ethyl carbonate with a polyol and an organic dicarboxylic acid Polyester polycarbonate polyol formed by acid reaction, and polyhydroxy compound and propylene carbonate A polycarbonate polyol obtained by transesterification of an ester. These may be used singly or in combination of two or more.

The polyol component may be used in combination with the above high molecular weight polyol. Glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6 - hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, 1,4-double (2 - hydroxyethoxy)benzene, trimethylolpropane, glycerol, 1,2,6-hexanetriol, neopentyl alcohol, tetramethylolcyclohexane, methyl glucoside, sorbitol, mannose Low molecular weight polyols such as alcohol, galactitol, sucrose, 2,2,6,6-tetrakis (hydroxymethyl)cyclohexanol, diethanolamine, N-methylethanolamine, and triethanolamine. Further, it may be used in combination with a low molecular weight polyamine such as ethylenediamine, toluenediamine, diphenylmethanediamine, or diethylenetriamine. Further, it may be used in combination with an alcoholamine such as monoethanolamine, 2-(2-aminoethylamine)ethanol or monopropanolamine. These low molecular weight polyols, molecular weight polyamines, and the like may be used alone or in combination of two or more. The mixing amount of the low molecular weight polyol or the low molecular weight polyamine or the like is not particularly limited and is appropriately determined depending on the characteristics required for the polishing pad (abrasive layer) to be produced.

When a polyurethane foam is produced by a prepolymer method, a chain extender is used. Used for hardening of prepolymers. The chain extender is an organic compound having at least two active hydrogen groups, and examples of the active hydrogen group include a hydroxyl group, a primary or secondary amine group, a thiol group (SH), and the like. Specifically, for example, 4,4'-methylenebis(o-chloroaniline) (MOCA), 2,6-dichloro-p-phenylenediamine, 4,4'-methylene bis (2,3- Dichloroaniline), 3,5-bis(methylthio)-2,4-toluenediamine, 3,5-bis(methylthio)-2,6-toluenediamine, 3,5-diethyl Toluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, 1,3-propanediol-di-p-aminobenzoate, polytetramethylene glycol-two pairs Ammonium benzoate, 4,4'-diamine-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamine-3,3'-diisopropyl-5 , 5'-dimethyldiphenylmethane, 4,4'-diamine-3,3',5,5'-tetraisopropyldiphenylmethane, 1,2-bis(2-aminophenylthio) Ethane, 4,4'-diamine-3,3'-diethyl-5,5'-dimethyldiphenylmethane, N-N'-di(secondary butyl)-4,4'-diamine Diphenylmethane, 3,3'-diethyl-4,4'-diamine diphenylmethane, meta-derivative diamine, N,N'-di(secondary butyl)-p-phenylenediamine, m-phenylenediamine And polyamines such as diamines and the like, or the above low molecular weight polyols or low molecular weight polyamines. These may be used alone or in combination of two or more.

Isocyanate component, polyol component and chain extender in the present invention The ratio varies depending on the molecular weight of each of them or the physical properties required for the polishing pad. In order to obtain a polishing pad having the desired polishing characteristics, the isocyanate group number of the isocyanate component is preferably 0.80 to 1.20, and 0.99 to the total active hydrogen group (hydroxyl + amine group) of the polyol component and the chain extender. 1.15 is better. If the number of isocyanate groups is outside the above range, it will result in poor curing and the desired specific gravity and hardness will not be obtained, and the polishing characteristics will be lowered.

The polyurethane foam can be a known polymer such as a melt method or a solution method. It is produced by an amine esterification technique, but it is preferably produced by a melt method in consideration of factors such as cost and working environment.

Polyurethane foam can be extracted by prepolymer method and direct polymerization method. a physical property of a polyurethane resin prepared by a method in which a prepolymer of an isocyanate is synthesized from an isocyanate component and a polyol component, and a prepolymer method in which a chain extender reacts with the prepolymer is prepared in advance. Good, so it is better than the above two methods.

A method for producing a polyurethane foam, which may be a hollow bead The method, the mechanical foaming method, the chemical foaming method, and the like are exemplified.

Further, it is particularly preferable to use a mechanical foaming method using a quinoid type surfactant which is a copolymer of a polyalkyl hydrazine and a polyether and which does not have an active hydrogen group.

Further, stabilizers such as antioxidants, lubricants, pigments, fillers, antistatic agents, and other additives may be added as necessary.

The polyurethane foam of the polishing layer constituting material may be of a closed cell type or a continuous cell type.

The manufacture of the polyurethane foam can be carried out in a batch production method in which the components are weighed and put into a container and stirred, and the mixture can be continuously supplied to the components and the non-reactive gas in a stirring device, and then stirred, and the bubble dispersion liquid is sent out to form a continuous molded product. ways to produce.

Further, the prepolymer of the raw material of the polyurethane foam may be placed in a reaction vessel, and then the chain extender is added and stirred, and then injected into a mold of a predetermined size to form a block, and the block is formed by using a planer or A method of slicing a band saw-like slicer or forming a sheet shape at the stage of the aforementioned casting. Further, the resin as a raw material may be dissolved and extruded into a shape by a T-die to directly obtain a sheet-like polyurethane foam.

The average bubble diameter of the polyurethane foam is preferably from 30 to 80 μm, more preferably from 30 to 60 μm. When it is out of this range, there exists a tendency for the grinding speed to fall, or the planarity (flatness) of the to-be-polished material (wafer) after grinding to fall.

The specific gravity of the polyurethane foam is preferably from 0.5 to 1.3. If the specific gravity is less than 0.5, the surface strength of the abrasive layer tends to decrease, and the plane of the material to be polished Reduced sex. On the other hand, when it is more than 1.3, the number of bubbles on the surface of the polishing layer is reduced, and although the planarity is good, the polishing rate tends to decrease.

The hardness of the aforementioned polyurethane foam should be ASKER D type hard The measurement is 40 to 75 degrees. If the hardness measured by the ASKER D-type hardness tester is less than 40 degrees, the flatness of the material to be polished is lowered. If it is greater than 75 degrees, the flatness is good, but the uniformity (homogeneity) of the material to be polished tends to decrease.

The abrasive surface of the abrasive layer in contact with the material to be polished is preferably used In order to maintain and replace the uneven structure of the polishing liquid. The polishing layer composed of the foam has many openings on the polishing surface and has the function of holding and replacing the polishing liquid. However, by forming the uneven structure on the polishing surface, the polishing liquid can be maintained and replaced more efficiently, and the prevention can be prevented. The material to be ground is adsorbed to damage the material to be polished. The uneven structure is not particularly limited as long as it can maintain and replace the shape of the polishing liquid, for example, an XY elongated groove, a concentric circular groove, a non-through hole, a polygonal column, a cylinder, a spiral groove, An eccentric circular groove, a radial groove, and a combination of the grooves. Further, the uneven structure is generally regular, but the groove pitch, the groove width, the groove depth, and the like may be changed every range in order to maintain and replace the polishing liquid.

The shape of the polishing layer is not particularly limited and may be circular or Narrow and long. The size of the polishing layer can be appropriately adjusted according to the grinding device to be used. The diameter of the circular shape is about 30 to 150 cm, and the length of the elongated shape is about 5 to 15 m and the width is about 60 to 250 cm.

The thickness of the polishing layer is not particularly limited, but is usually about 0.8~ 4mm, and preferably 1.2~2.5mm.

The polishing layer is provided with light for performing polishing Learn the transparent components of endpoint detection. The transparent member is embedded in the opening provided in the polishing layer, and is fixed by the subsequent member under the polishing layer.

The laminated polishing pad is bonded with a hot melt adhesive and supports Layer to make.

The aforementioned support layer is used to complement the characteristics of the abrasive layer. Support layer A layer (buffer layer) having a lower modulus of elasticity than the polishing layer or a layer having a higher modulus of elasticity than the polishing layer (highly elastic layer) may be used. In the buffer layer system CMP, it is necessary to make both the planarity and the uniformity in the trade-off relationship. The term "planarity" refers to the flatness of the pattern portion after the material to be polished having minute irregularities is formed during the formation of the polishing pattern, and the uniformity refers to the uniformity of the entire material to be polished. By improving the planarity by the characteristics of the polishing layer, the uniformity is improved by the characteristics of the buffer layer. In the CMP, in order to suppress the occurrence of cracks, a soft polishing layer is used, and a high elastic layer is used to improve the flattening property of the polishing pad. Further, by using the highly elastic layer, it is possible to suppress excessive cutting of the edge portion of the material to be polished.

The thickness of the aforementioned support layer is not particularly limited, but is preferably 0.4~2mm, preferably 0.6~1.5mm, and 0.7~1.3mm is better.

The aforementioned buffer layer may, for example, be a polyester non-woven fabric or a nylon non-woven fabric. Non-woven fabric such as cloth and acrylic non-woven fabric; impregnated resin non-woven fabric such as polyester non-woven fabric impregnated with polyurethane; polymer resin foam such as polyurethane foam and polyethylene foam; rubber such as butadiene rubber and isoprene rubber Resin; photosensitive resin, etc.

The aforementioned high elastic layer may, for example, be polyethylene terephthalate thin Polyester film such as film and polyethylene naphthalate film; polyolefin film such as polyethylene film and polypropylene film; nylon film.

When a transparent member is provided on the polishing layer, it is preferable to provide an opening for allowing light to pass through the support layer.

The hot-melt adhesive sheet may be an adhesive layer formed of a hot-melt adhesive or a double-sided tape provided with the above-mentioned adhesive layer on both sides of the substrate.

The polyester-based hot-melt adhesive of the material of the adhesive layer contains 2 to 10 parts by weight of a ring having 2 or more epoxy propyl groups in one molecule, based on 100 parts by weight of the polyester resin of the base polymer. Oxygen resin.

The polyester resin can be obtained by a polymerization polymerization of an acid component and a polyhydric alcohol, but it is particularly preferred to use a crystalline polyester resin.

The acid component may, for example, be an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid. Only one of these acid components may be used, or two or more types may be used in combination.

Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic anhydride, α-naphthalene dicarboxylic acid, β-naphthalene dicarboxylic acid, and ester formations thereof.

Specific examples of the aliphatic dicarboxylic acid include, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, sebacic acid, undecylenic acid, dodecanedicarboxylic acid, and esters thereof. Form a body, etc.

Specific examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.

Further, as the acid component, a polyvalent carboxylic acid such as maleic acid, fumaric acid, dimer acid, trimellitic acid or pyroic acid may be used in combination.

The polyol component may, for example, be an aliphatic diol or a diol such as an alicyclic diol or a polyhydric alcohol. It is possible to use only one of these polyol components, or Use two or more types together.

Specific examples of the aliphatic diol include ethylene glycol, 1,2-propane. Glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, new Pentandiol, 3-methylpentanediol, 2,2,3-trimethylpentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and the like.

Specific examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogen. For example, bisphenol A or the like is used.

Examples of the polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, and neopentylol.

The crystalline polyester resin can be synthesized by a known method. E.g, In addition, a melt polymerization method in which a raw material and a catalyst are prepared and heated at a temperature equal to or higher than the melting point of the product, a solid phase polymerization method in which the temperature is lower than the melting point of the product, a solution polymerization method using a solvent, or the like may be employed.

The melting point of the crystalline polyester resin is preferably from 100 to 200 °C. Melting point When the temperature reaches 100 ° C, the adhesion of the hot melt adhesive is lowered by the heat generated during the polishing, and when the temperature exceeds 200 ° C, the temperature of the hot melt adhesive is increased, so that the laminated polishing pad is warped. The tendency of the abrasive properties to cause adverse effects.

Further, the number average molecular weight of the crystalline polyester resin is preferably 5000~50000. When the number average molecular weight is less than 5,000, the mechanical properties of the hot-melt adhesive are lowered, so that sufficient adhesion and durability cannot be obtained, and when it is more than 50,000, when a synthetic crystalline polyester resin is synthesized, gelation or the like is produced. Disadvantages, or a tendency to degrade as a hot melt adhesive.

The epoxy resin may, for example, be a bisphenol A type epoxy resin or a bromine Bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, styrene epoxy resin, biphenyl epoxy resin, bisphenol A novolac epoxy resin, a cresol novolac type epoxy resin, a diamine biphenylmethane type epoxy resin, and a polyphenylene epoxy resin such as hexahydrophenylene glycol; a ruthenium containing epoxy resin, trisepoxypropyl isocyanate, An aromatic epoxy resin such as an epoxy resin containing a heteroaromatic ring (for example, a triazabenzene ring); an aliphatic epoxy propyl ether epoxy resin; an aliphatic epoxypropyl ester epoxy resin; Non-aromatic epoxy resin such as alicyclic epoxy propyl ether type epoxy resin or alicyclic epoxy propyl ester type epoxy resin. One type of these epoxy resins may be used alone or two or more types may be used in combination.

Among these epoxy resins, a cresol novolac type epoxy resin is preferably used from the viewpoint of adhesion to the polishing layer during polishing.

The epoxy resin is added in an amount of 2 to 10 parts by weight, and preferably 3 to 7 parts by weight, based on 100 parts by weight of the polyester resin of the base polymer.

The polyester-based hot-melt adhesive may contain a softener such as an olefin resin, a known additive such as an adhesion-imparting agent, a filler, a stabilizer, and a coupling agent. Further, it may contain an inorganic filler such as talc.

The polyester-based hot melt adhesive is prepared by mixing at least the polyester resin, the epoxy resin, or the like by any method. For example, by a single-axis extruder, an intermeshing type parallel parallel shaft twin-axis extruder, an intermeshing type anisotropic parallel shaft twin-axis extruder, an intermeshing type anisotropic axis double-axis extruder, a non-intermeshing type double Extruder or kneading machine for shaft extruder, incomplete meshing type twin-screw extruder, co-twisting and extrusion press, planetary gear type extruder, transfer mixing extruder, roller extruder, etc. The raw materials are mixed to prepare.

The melting point of the polyester-based hot melt adhesive is preferably from 100 to 200 °C.

Further, the specific gravity of the polyester-based hot-melt adhesive is preferably from 1.1 to 1.3.

Further, the melt flow index (MI) of the polyester-based hot-melt adhesive is preferably 16 to 26 g/10 min at a temperature of 150 ° C and a load of 2.16 kg.

The method of bonding the polishing layer and the support layer is not particularly limited, and an adhesive layer formed of a polyester-based hot-melt adhesive is laminated on the support layer (or the polishing layer), and the adhesive layer is heated and heated by a heater. Then, a method in which the polishing layer (or the support layer) is laminated on the molten adhesive and punched is exemplified. The pressing pressure is not particularly limited, but it is preferably 0.1 to 1.0 MPa.

The thickness of the adhesive layer formed of the hot melt adhesive is preferably from 10 to 200 μm, more preferably from 30 to 100 μm. When the thickness of the subsequent layer is less than 10 μm, the high-temperature polishing agent has a high temperature resistance during the polishing, and the durability of the hot-melt adhesive to the "displacement" during polishing is insufficient. Therefore, the polishing layer and the support layer are easily peeled off. On the other hand, when it is more than 200 μm, the transparency is lowered, so that there is a problem in the detection accuracy of the laminated polishing pad provided with the transparent member for optical detection.

It is also possible to use a double-sided tape having the above-mentioned adhesive layer on both sides of the substrate instead of the adhesive layer formed of the hot-melt adhesive. The slurry can be prevented from impregnating to the support layer side by the substrate, and peeling between the support layer and the adhesive layer can be prevented.

Examples of the substrate include polyester films such as polyethylene terephthalate film and polyethylene naphthalate film; polyolefin films such as polyethylene film and polypropylene film; and nylon films. Among them, a polyester film excellent in water permeable property is preferably used.

The surface of the substrate can also be subjected to corona treatment, plasma treatment, etc. Processing.

The thickness of the substrate is not particularly limited, but is transparent and soft. From the viewpoints of properties, rigidity, and dimensional stability during heating, it is preferably from 10 to 180 μm.

When double-sided tape is used, the thickness of the aforementioned adhesive layer is preferably 10~200μm, preferably 30~100μm.

Moreover, the laminated polishing pad can also bond the abrasive layer with the adhesive layer The support layer is produced.

The support layer with the adhesive layer is applied to one side of the support layer The polyester-based hot-melt adhesive is cured and hardened to form an adhesive layer directly on the support layer. The support layer is preferably a polyurethane foam sheet having a skin layer on the surface on which the adhesive layer is provided. Further, the polyurethane foam sheet is preferably formed of a thermosetting polyurethane. Further, for the same reason as described above, the thickness of the adhesive layer is preferably from 10 to 200 μm, more preferably from 30 to 100 μm.

a method of bonding an abrasive layer to a support layer with an adhesive layer There is no particular limitation, and a method of heating and melting the adhesive layer with the support layer of the adhesive layer by a heater, and then laminating the polishing layer on the molten adhesive and pressing it is exemplified. The pressing pressure is not particularly limited, but it is preferably 0.1 to 1.0 MPa.

The laminated polishing pad can also be provided with double-sided tape on the surface next to the platform.

Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples.

[Measurement, evaluation method]

(number average molecular weight)

The number average molecular weight is determined by GPC (gel permeation chromatography) and converted to standard polystyrene.

GPC device: manufactured by Shimadzu Corporation, LC-10A

Chromatography column: manufactured by Polymer Laboratories, and connected (PLgel, 5μm, 500Å), (PLgel, 5μm, 100Å), and (PLgel, 5μm, 50Å) three chromatography columns for use.

Flow rate: 1.0ml/min

Concentration: 1.0g/l

Injection volume: 40μl

Chromatography column temperature: 40 ° C

Precipitate: tetrahydrofuran

(Measurement of melting point)

The melting point of the polyester-based hot-melt adhesive was measured using a TOLEDO DSC822 (manufactured by METTLER Co., Ltd.) at a temperature elevation rate of 20 ° C/min.

(measurement of specific gravity)

According to JIS Z8807-1976. The adhesive layer formed of the polyester-based hot-melt adhesive was cut into a strip shape (thickness: arbitrary) of 4 cm × 8.5 cm to prepare a sample for measuring specific gravity, and the temperature was 23 ° C ± 2 ° C and the humidity was 50% ± Allow to stand for 16 hours in a 5% environment. In the measurement, the specific gravity was measured using a hydrometer (manufactured by Sartorius Co., Ltd.).

(Measurement of melt flow index (MI))

The melt flow index of the polyester-based hot melt adhesive at 150 ° C and 2.16 kg was measured in accordance with ASTM-D-1238.

(following the determination of strength)

Three samples of width 25 mm × length 200 mm were cut out from the fabricated laminated polishing pad, and the polishing layer and the support layer of each sample were stretched at a stretching angle of 180° and a stretching speed of 300 mm/min, and the measurement was followed. Strength (N/25mm). The average of the three samples is shown in Table 1. Further, the peeling state of the sample at this time was confirmed. Further, hydrogen peroxide water was added to a slurry (manufactured by Cabot Co., Ltd., W2000) to adjust the concentration to 4% by weight to prepare a polishing slurry. The sample was immersed in the above-mentioned polishing slurry adjusted to 80 ° C for 8 hours, and then the subsequent strength was measured in the same manner as described above, and the peeling state was confirmed. Repeat this operation 5 times.

Manufacturing example 1

1229 parts by weight of toluene isocyanate (2,4-body/2,6-body=80/20 mixture), 272 parts by weight of 4,4'-dicyclohexylmethane diisocyanate, 1901 parts by weight of number average molecular weight 1018 polytetramethylene ether glycol, 198 parts by weight of diethylene glycol was placed in a container, and reacted at 70 ° C for 4 hours to obtain a prepolymer having an isocyanate group.

100 parts by weight of the prepolymer and 3 parts by weight of a quinone type surfactant (SH-192, manufactured by Dow Corning Toray ‧ Silicone Co., Ltd.) were added to the polymerization vessel, and adjusted to 80 ° C, and defoamed under reduced pressure. . Subsequently, the stirring blade was vigorously stirred at a rotation number of 900 rpm for about 4 minutes to carry the bubbles into the reaction system. Further, 21 parts by weight of Ethacure 300 (manufactured by Albemarle, 3,5-bis(methylthio)-2,6-toluenediamine and 3,5-bis(methylthio)-2) having a pre-adjusted temperature of 70 ° C was added. , a mixture of 4-toluenediamine). The mixture was stirred for about 1 minute and then poured into a disc type open mold (molding container). When the mixture loses fluidity, it is placed in an oven and hardened at 100 ° C for 16 hours. A polyurethane foam block was obtained.

The polyurethane foam block which was heated to 80 ° C was sliced using a microtome (VGW-125, manufactured by Amitec Co., Ltd.) to obtain a polyurethane foam sheet (average bubble diameter: 50 μm, specific gravity: 0.86, hardness: 52 degrees). . Next, the sheet was subjected to surface rubbing treatment using a polisher (manufactured by Amitec Co., Ltd.) until the thickness became 2 mm, thereby forming an integrated sheet having a thickness precision. The sheet subjected to the buffing treatment was punched to a diameter of 60 cm, and a concavity circle having a groove width of 0.25 mm, a groove pitch of 1.5 mm, and a groove depth of 0.6 mm was performed on the surface using a groove processing machine (manufactured by Techno Corporation). The groove is processed to form an abrasive layer.

Example 1

On a PET film (E5200, manufactured by TOYOBO Co., Ltd.) having a thickness of 50 μm which was subjected to corona treatment on both sides, 100 parts by weight of a laminate containing a crystalline polyester resin (VYLON GM420, manufactured by TOYOBO Co., Ltd.), and 5 parts by weight in one molecule An adhesive layer (thickness 50 μm) formed of a polyester-based hot-melt adhesive having two or more epoxy ketone o-cresol novolak type epoxy resins (NEC4400, manufactured by NIPPON KAYAKU Co., Ltd.) and using an infrared heater The surface of the adhesive layer was heated to 150 ° C to melt the adhesive layer. Then, using a laminator having a pressure of 0.6 MPa, a polishing layer prepared in accordance with Production Example 1 was laminated on the molten adhesive layer at a conveying speed of 1 m/min, and pressed to adhere thereto, thereby obtaining a laminated body A (grinding) Layer/adhesive layer/PET film).

On the release film, the above-mentioned adhesive layer (thickness: 50 μm) was formed, and the surface of the adhesive layer was heated to 150 ° C using an infrared heater to melt the adhesive layer. Then, using a laminator with a pressure of 0.6 MPa, the conveying speed is 1 m/min. The release film was peeled off, and a support layer (NIPPALAY EXT, manufactured by NHK SPRING Co., Ltd.) formed of the laminate A and the foamed polyurethane was laminated on the melted adhesive layer, and pressure was applied thereto to form a laminate. Body B (abrasive layer/adhesive layer/PET film/adhesive layer/support layer).

Then, a pressure-sensitive double-sided tape (442JA manufactured by 3M Company) was bonded to the support layer of the laminated body B by using a laminator to prepare a laminated polishing pad.

Further, the polyester-based hot-melt adhesive had a melting point of 142 ° C, a specific gravity of 1.22, and a melt flow index of 21 g/10 min.

Example 2

An adhesive layer (thickness: 50 μm) formed of the polyester-based hot-melt adhesive described in Example 1 was formed on a PEN film (Teonex Q83, manufactured by Teijin DuPont Film Co., Ltd.) having a thickness of 50 μm which was subjected to corona treatment on both sides, and then A laminated polishing pad was produced in the same manner as in Example 1.

Example 3

In the same manner as in Example 1, 100 parts by weight of a crystalline polyester resin (VYLON GM420, manufactured by TOYOBO Co., Ltd.), and 2 parts by weight of an o-cresol novolac having 2 or more epoxy propyl groups in one molecule were used. A laminated polishing pad was produced in the same manner as in Example 1 except that a polyester-based hot-melt adhesive of a type epoxy resin (manufactured by NIPPON KAYAKU Co., Ltd., EOCN 4400) was used. Further, the polyester-based hot-melt adhesive had a melting point of 140 ° C, a specific gravity of 1.24, and a melt flow index of 26 g/10 min.

Example 4

In addition to the use in Example 1, 100 parts by weight of a crystalline polyester resin (VYLON GM420, manufactured by TOYOBO Co., Ltd.), and 10 parts by weight were used. A laminate was formed in the same manner as in Example 1 except that a polyester-based hot-melt adhesive having two or more epoxy ketone o-cresol novolac type epoxy resins (EOCN4400, manufactured by NIPPON KAYAKU Co., Ltd.) was used in one molecule. Grinding pad. Further, the polyester-based hot-melt adhesive had a melting point of 145 ° C, a specific gravity of 1.19, and a melt flow index of 16 g/10 min.

Example 5

100 parts by weight of a crystalline polyester resin (VYLON GM420, manufactured by TOYOBO Co., Ltd.) was applied to a skin layer of a thermosetting polyurethane foam sheet (NIPPALAY EXT, thickness: 0.8 mm, manufactured by NHK SPRING Co., Ltd.) having a skin layer on one side. And 5 parts by weight of a polyester-based hot-melt adhesive having an ortho-cresol novolac type epoxy resin (EOCN4400, manufactured by NIPPON KAYAKU Co., Ltd.) having two or more epoxy propyl groups in one molecule, and hardening it An adhesive layer (thickness: 75 μm) was formed to prepare a foamed sheet with an adhesive layer.

The surface of the adhesive layer of the foamed sheet with the adhesive layer was heated to 150 ° C using an infrared heater to melt the adhesive layer. Then, using a laminator having a pressure of 0.6 MPa, a layer formed on the melted adhesive layer and pressed in accordance with the polishing layer prepared in Production Example 1 was adhered at a conveying speed of 0.8 m/min to obtain a laminate (grinding) Layer/adhesive layer/foam sheet).

Then, a pressure-sensitive double-sided tape (manufactured by 3M Company, 442JA) was bonded to the foamed sheet of the laminate using a laminator to prepare a laminated polishing pad.

Further, the polyester-based hot-melt adhesive had a melting point of 142 ° C, a specific gravity of 1.22, and a melt flow index of 21 g/10 min.

Comparative example 1

In addition to the use of 100 parts by weight of crystalline polyester in Example 1 Resin (VYLON GM420, manufactured by TOYOBO Co., Ltd.), and 1 part by weight of polyester-based heat of o-cresol novolak-type epoxy resin (manufactured by NIPPON KAYAKU Co., Ltd., EOCN4400) having two or more epoxy propyl groups in one molecule A build-up polishing pad was produced in the same manner as in Example 1 except for the flux. Further, the polyester-based hot-melt adhesive had a melting point of 139 ° C, a specific gravity of 1.25, and a melt flow index of 29 g/10 min.

Comparative example 2

In the first embodiment, 100 parts by weight of a crystalline polyester resin (VYLON GM420, manufactured by TOYOBO Co., Ltd.), and 18 parts by weight of o-cresol novolac having 2 or more epoxy propyl groups in one molecule were used. A laminated polishing pad was produced in the same manner as in Example 1 except that a polyester-based hot-melt adhesive of a type epoxy resin (manufactured by NIPPON KAYAKU Co., Ltd., EOCN 4400) was used. Further, the polyester-based hot-melt adhesive had a melting point of 147 ° C, a specific gravity of 1.18, and a melt flow index of 15 g/10 minutes.

[Table 1]

The laminated polishing pads of Examples 1 to 5 were immersed in high even for a long time. In the case of the temperature slurry, no peeling at the interface of the adhesive layer occurred. On the other hand, in Comparative Examples 1 and 2, peeling at the interface of the adhesive layer occurred when immersed in the polishing slurry at a high temperature for a long period of time. From these results, it is understood that when the laminated polishing pad is produced by using the hot-melt adhesive sheet of the present invention, stable polishing performance can be obtained even when it is heated to a high temperature due to long-time polishing.

Claims (9)

A hot-melt adhesive sheet for a laminated polishing pad, which is used for laminating an abrasive layer and a support layer, wherein the polishing layer is formed of a polyurethane resin, and the support layer is a polyester film, and the aforementioned heat fusion is continued The polyester-based hot-melt adhesive contains 2 to 10 parts by weight of a cresol novolak type ring having 2 or more epoxy propyl groups in one molecule, based on 100 parts by weight of the polyester resin of the base polymer. Oxygen resin. A hot-melt adhesive sheet for a laminated polishing pad according to the first aspect of the invention, wherein the polyester resin is a crystalline polyester resin. The hot-melt adhesive sheet for a laminated polishing pad according to the first aspect of the patent application, wherein the polyester-based hot-melt adhesive has a melting point of 100 to 200 ° C, a specific gravity of 1.1 to 1.3, and a temperature of 150 ° C and a load of 2.16. The melt flow index under the conditions of kilograms is 16 to 26 g/10 minutes. The hot-melt adhesive sheet for a laminated polishing pad according to the first aspect of the invention, wherein the hot-melt adhesive sheet has an adhesive layer formed of the hot-melt adhesive on both sides of a substrate which is subjected to easy subsequent treatment. double-sided tape. A hot-melt adhesive sheet for a laminated polishing pad according to claim 4, wherein the foregoing easy treatment is corona treatment or plasma treatment. A support layer with an adhesive layer for a build-up polishing pad, which is provided on one side of a support layer, and has an adhesive layer obtained by coating a polyester-based hot-melt adhesive and hardening it, and the polyester is thermally fused The agent is contained in an amount of 2 to 10 parts by weight based on 100 parts by weight of the polyester resin of the base polymer in one molecule. A cresol novolac type epoxy resin having two or more epoxy propyl groups, and the support layer is a polyurethane foam sheet having a skin layer on a surface on which the above-mentioned adhesive layer is provided. The support layer of the adhesive layer for a build-up polishing pad is attached to the sixth aspect of the patent application, wherein the polyester resin is a crystalline polyester resin. The support layer of the adhesive layer for a laminated polishing pad is provided in the sixth aspect of the patent application, wherein the polyester-based hot-melt adhesive has a melting point of 100 to 200 ° C, a specific gravity of 1.1 to 1.3, and a temperature of 150 ° C and The melt flow index is 16 to 26 g/10 min under a load of 2.16 kg. The support layer of the adhesive layer for a build-up polishing pad is attached to the sixth aspect of the patent application, wherein the polyurethane foam sheet is formed of a thermosetting polyurethane.